Developing novel synthetic strategies to construct crystalline polymeric materials with excellent chemical stability and high carbon capture capacity has become a challenging process. Herein, we report the synthesis of two novel 2D benzobisoxazole-linked covalent organic frameworks (BBO-COFs) utilizing C3-symmetric formyl- and C2-symmetric o-aminophenol-substituted molecular building blocks. The BBO-COFs exhibit excellent water stability, high surface areas, and great CO2 uptake capacities. This general synthetic method affords the opportunity to prepare ordered BBO-based polymeric materials for carbon capture, chemical sensing, and organic electronic applications.